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This paper is the first of two back-to-back works, whose goal is to update the existing line positions and intensities spectroscopic parameters for the 5.8 µm region of nitric acid in the HITRAN or GEISA spectroscopic databases. This first study is devoted to the generation of first linelists for the ν 2 +ν 9 -ν 9 , ν 2 +ν 7 -ν 7  and ν 2 +ν 6 -ν 6  hot bands in the 5.8 µm region, whereas the second study will concern the positions and intensities for the ν 2  band centred at 1709.567 cm −1 . High-resolution Fourier transform spectra were recorded in the 5.8 µm and in the 4.2–4.6 µm spectral ranges. The identification of the ν 2 +ν 9 , ν 2 +ν 7  and ν 2 +ν 6  bands of HNO 3  at 2165.0036, 2285.9657 and 2351.216 cm −1 , respectively, was performed, and several assignments were confirmed by searching for ν 2 +ν 9 -ν 9  and ν 2 +ν 7 -ν 7  transitions within those of ν 2  at 5.8 µm. Both ν 2 +ν 6  and ν 2 +ν 9  bands are highly perturbed. Surprisingly, both ν 2 +ν 9  and ν 2 +ν 9 -ν 9  bands exhibit large amplitude torsional splittings of ∼0.043 cm −1 . This is presumed to be due to the existence of an anharmonic resonance that couples together the 2 1 9 1  energy levels with those of a dark state involving high excitation in the ν 9  large amplitude OH torsional mode.

molecular physics

First analysis of the ν 2 +ν 7  and ν 2 +ν 9  and ν 2 +ν 6  combination bands of HNO 3 : evidence of perturbations due to large amplitude OH torsion in the 2 1 9 1  excited state